CN109071398A

CN109071398A - The method for generating alpha, beta-unsaturated carboxylic acid and its salt

Info

Publication number: CN109071398A
Application number: CN201780022267.2A
Authority: CN
Inventors: M·哈维卡; M·麦克丹尼尔
Original assignee: Chevron Phillips Chemical Co LLC
Current assignee: Chevron Phillips Chemical Co LLC
Priority date: 2016-04-06
Filing date: 2017-04-04
Publication date: 2018-12-21
Anticipated expiration: 2037-04-04
Also published as: EP3426627A1; CN115433075A; WO2017176669A1; CN109071398B

Abstract

The open method that alpha, beta-unsaturated carboxylic acid or its salt such as acrylic acid are generated using treated soild oxide.The treated soild oxide can be the soild oxide of calcining solid oxide, the soild oxide by metal processing or the chemical modification by metal processing, and illustrative example may include the aluminium oxide handled by sodium, by the aluminium oxide of Calcium treatment, the aluminium oxide by zinc processing, the sulfated alumina by sodium processing, the fluorinated aluminium oxide and similar material by coated with silica handled by sodium.

Description

The method for generating alpha, beta-unsaturated carboxylic acid and its salt

Background technique

Most of compound industrially synthesized is prepared by one group of limited precursor, and source is finally fossil fuel.Make It is nontoxic, a large amount of and inexpensive C with renewable resource, such as carbon dioxide₁Synthesis unit by for beneficial carbon dioxide and The coupling of alkene is greatly kept, because a people, which can be envisaged, directly prepares acrylate and carboxylic acid by this method.Currently, Acrylic acid is generated via the oxidation of two stage propylene.Acrylic acid directly will indicate phase from the generation of carbon dioxide and ethylene Propylene is significantly improved due to caused by the more high availability of ethylene and carbon dioxide, recyclable materials (CO₂) in synthesis Use and currently the two step oxygen just practiced close the substitution of method.Therefore, the present invention be directed to these purposes.

Summary of the invention

The method for generating alpha, beta-unsaturated carboxylic acid or its salt is disclosed herein.The expression of these methods is changed compared with even method Kind, the even method generates bad yield and has challenging separation (separation/isolation) program, Partially due to reaction carries out in organic solvent, make required α, the separation of beta-unsaturated carboxylic acid (for example, acrylic acid) is difficult.It compares Under, method disclosed herein is mentioned using solid promoter (or solid activating agent, such as treated soild oxide) For having the advantages that different heterogeneous systems in terms of being easy to separate required product from catalytic promoter.In addition, solid promotes Agent can produce the unexpectedly high yield of required acrylate or alpha, beta-unsaturated carboxylic acid (such as acrylic acid).

The method of various aspects according to the present invention, such a generation α, beta-unsaturated carboxylic acid or its salt may include:

(1) make following contact

(a) metal lactone (metallalactone)；

(b) diluent；With

(c) solid promoter (for example, treated soild oxide)；

(2) addition product for the alpha, beta-unsaturated carboxylic acid being adsorbed onto solid promoter is formed；And

(3) addition product that processing is adsorbed onto solid promoter is to generate alpha, beta-unsaturated carboxylic acid or its salt.

In another aspect of this invention, it provides and generates α, the method for beta-unsaturated carboxylic acid or its salt, and in this regard, The method may include:

(I) make following contact

(i) transition metal-ligand complex compound；

(ii) alkene；

(iii) carbon dioxide (CO₂)；

(iv) diluent；With

(v) solid promoter (for example, treated soild oxide)；And

(II) alpha, beta-unsaturated carboxylic acid or its described salt are formed.

But the method for carrying out metal lactone elimination reaction in another aspect of this invention, is provided, and in this regard, institute The method of stating may include:

(1) make following contact

(a) metal lactone；

(b) diluent；With

(c) solid promoter (for example, treated soild oxide)；And

(2) alpha, beta-unsaturated carboxylic acid or its salt are formed.

In these and other aspects, method disclosed herein can be used for generating such as acrylic acid or its salt.

Foregoing general description and described in detail below all provide example and only explanatory.Therefore, foregoing summary and Following implementation is not considered as restrictive.In addition, other than those of described herein, it is possible to provide feature or change Change.For example, some aspects can be for the combination of various features described in embodiment and sub-portfolio.

Definition

More clearly to define the term as used herein, provide defined below.Unless otherwise instructed, otherwise defined below suitable For the disclosure.If term, can be using from " IUPAC chemistry art for not being specifically defined in the disclosure but herein Vocabulary compiles (IUPAC Compendium of Chemical Terminology) ", the definition of second edition (1997), as long as described Definition does not conflict with any other disclosure or definition used herein, or does not make to become not using any claim of the definition It is fixed or can not enable.Any definition or use just provided by any document for being incorporated herein by reference with Definition provided herein uses for conflict, based on definition or use provided herein.

Unless otherwise stated, although otherwise describing composition and method according to the various components of "comprising" or step aspect, But composition and method can be with " being mainly made of various components or step " or " being made of various components or step ".Citing comes It says, the accessible step in certain methods consistent with the present invention includes metal lactone, diluent and treated solid oxygen The component of compound；Alternatively, the accessible component being mainly made of metal lactone, diluent and treated soild oxide； Alternatively, the accessible component being made of metal lactone, diluent and treated soild oxide.

Term "one", "an" and it is " described " wish include a plurality of alternatives, for example, at least one.Citing comes It says, unless specified otherwise herein, otherwise " solid promoter ", " treated soild oxide " or the disclosure of " diluent " are beaten respectively Calculation covers one kind or more than a kind of solid promoter, the mixture of treated soild oxide or diluent or combination.

In general, using at " chemistry with Engineering News Record (Chemical and Engineering News) ", 63 (5), Indicated numbering plan comes indicator element group in the periodic table of elements version published in 27,1985.In some instances, first The common name for distributing to group can be used to indicate for plain group；Such as the 1st alkali metal of race's element, the 2nd race's element alkaline-earth metal, 3rd race is to the transition metal of the 12nd race's element and the halogen or halide of the 17th race's element.

Term " hydrocarbon " refers to the only compound containing carbon and hydrogen.Other identifiers may be used to indicate special groups in hydrocarbon In the presence of for example, the presence of the one or more halogen atoms for replacing equal amount hydrogen atom in hydrocarbon of halogenated hydrocarbons instruction.

As used herein, term " α, beta-unsaturated carboxylic acid " and its derivative, which refer to have, is connected to carbonylic carbon atom (band Have the carbon atom of double bond oxygen atom) on carbon-to-carbon double bond carbon atom.Optionally, α, beta-unsaturated carboxylic acid can contain other officials It can base and/or hetero atom.

For any specific compound disclosed herein or group, unless specified otherwise herein, any title for otherwise presenting or Structure be intended to cover to may originate from all configurational isomers thereofs of the specific collection of substituent group, regioisomer, stereoisomer and its Mixture.Unless specified otherwise herein, otherwise as to will be appreciated that furthermore title or structure cover all mappings different by one of ordinary skill in the art No matter structure body, diastereoisomer and with enantiomerism or other optical isomers (if present) of racemic form, And the mixture of stereoisomer.It for example, include pentane, 2- methyl-butan and 2,2- diformazan referring generally to pentane Base propane；It and include normal-butyl, sec-butyl, isobutyl group and tert-butyl referring generally to butyl.

Disclosed herein is various numberical ranges.Unless specified otherwise herein, otherwise when being disclosed herein or require any kind of model When enclosing, it is intended to the possible numerical value of every kind for individually disclosing or requiring this kind of range can reasonably cover, the end including the range The combination of point value and any subrange and the subrange wherein covered.In addition, all endpoints of range disclosed herein Value is approximation.Such as a representative example, the one or more steps for disclosing the method for the present invention in one aspect of the invention can be It is carried out at a temperature of in the range of 10 DEG C to 75 DEG C.This range, which should be interpreted that, covers " about " 10 DEG C in the range of 75 DEG C of " about " Temperature.

When using term " being substituted " description group, such as when referring to the analog of special groups being substituted, Intend the compound or group for describing to replace the hydrogen in the group or compound on any of them non-hydrogen portion-form, and intends It is unrestricted.Compound or group herein are also referred to as " being unsubstituted " or such as " non-by equal term Replace " it refers to, refer to original group or compound.Unless specified otherwise herein, otherwise " be substituted " be intended to it is unrestricted Property, and including inorganic substituent or organic substituent as those skilled technical personnel to understand the general.

Unless specified otherwise herein, otherwise term " product of contact ", " contact " etc. herein for describe component in any order, Merge or contact and maintain the composition and method of any time length in any way.For example, component can It is contacted and blending or mixing.In addition, unless specified otherwise herein, otherwise the contact of any component can be in composition as described herein With any other component of method presence or absence of lower progress.Combining additional material or component can be by any suitable Method carry out.In addition, term " product of contact " includes mixture, admixture, solution, slurries, reaction product etc. or its group It closes.Although " product of contact " can and usually include reaction product really, respective components do not need to react with each other.Similarly, term " contact " can be blended, be mixed, pulp, dissolution, reaction, processing or in addition contact in some other manner to refer to herein Material.

Although can be in practice or test of the invention using being similar to or be equivalent to approach described herein and material Any method and material, but typical method and material is described herein.

All publication and patent mentioned by this paper are incorporated herein by reference for describing and disclosing Such as the purpose of construct described in the publication and method, the construct and method are in combination with presently described The present invention is used together.

Specific embodiment

The present invention is usually to be directed to the method to form alpha, beta-unsaturated carboxylic acid or its salt.Suitable alpha, beta-unsaturated carboxylic acid Illustrative example is acrylic acid.

As disclosed herein, isomery method of the invention can provide the advantage different compared with homogeneous system, described uniform System is easy to separate (for example, solid- liquid separation technology) from solid catalysis promotor (for example, treated soild oxide) Required reaction product.In addition, and at the same time be not intended to be combined with following theory, it is believed that method of the invention also helps: Additional or auxiliary liquid alkali (for example, alkoxide, hydride or amine) does not need to carry out disclosed method.In addition, (for example, passing through Coupling part) it covalent bond or is fixed on the transition metal complex of solid carrier and does not need to carry out disclosed method.In addition, Isomery alkali comprising (for example, passing through coupling part) covalent bond or the organic basic part for being fixed on solid carrier do not need into The disclosed method of row.In addition, have be dissolved in reaction medium organic base consume isomery alkalinity reservoir (for example, NaH it) does not need to carry out disclosed method.And finally, fragrant base oxide (for example, fluorobenzene phenates) does not need to carry out institute's public affairs The method opened.

In addition, and at the same time being not intended to be combined with following theory, it is believed that disclosed herein certain by processing Soild oxide through combined bronsted lowry acids and bases bronsted lowry functionality (for example, bearing department through combined lewis acid (Lewis acid) and cloth Special alkali (Base) feature) unexpected height can be generated in metal lactone elimination reaction and carboxylic acid are formed and reacted Yield.

Solid promoter

Be commonly used for method disclosed herein solid promoter may include it is following (or be substantially made up of or It is made up of): soild oxide, clay or column clay or combinations thereof.For example, it is contemplated that two or more solids promote Into the mixture or combination some aspects for use in the present invention of agent.In general, term solid promoter herein can be with solid Activator is used interchangeably.

According on one side, solid promoter may include alkaline accelerator, for example, can be used as the solid promoter of alkali.Alkali The representative and unrestricted example of property promotor may include aluminium oxide, titanium dioxide, zirconium oxide, magnesia, boron oxide, Calcium oxide, zinc oxide, silica-alumina, aluminium oxide, silica-titania, titanium dioxide by coated with silica Silicon-zirconium oxide, silica-magnesia, aluminium oxide-titanium dioxide, aluminium oxide-zirconium oxide, zinc aluminate, alumina-boron oxide, Silica-boria, aluminum phosphate, aluminate or phosphate, aluminate or phosphate-silica, magnesium aluminate, titania-zirconia etc. with And combinations thereof.Solid promoter may include lewis promoters according to another aspect,.The representativeness of lewis promoters is simultaneously And unrestricted example may include silica, aluminium oxide, titanium dioxide, zirconium oxide, magnesia, boron oxide, calcium oxide, oxygen Change zinc, silica-alumina, aluminium oxide, silica-titania, silica-zirconia by coated with silica Zirconium, silica-magnesia, aluminium oxide-titanium dioxide, aluminium oxide-zirconium oxide, zinc aluminate, alumina-boron oxide, titanium dioxide Silicon-boron oxide, aluminum phosphate, aluminate or phosphate, aluminate or phosphate-silica, magnesium aluminate, titania-zirconia etc. and its group It closes.According to another aspect, solid promoter may include that cloth bears the special alkali promotor of department.Cloth bear the representativeness for taking charge of special alkali promotor and Unrestricted example may include aluminium oxide, titanium dioxide, zirconium oxide, magnesia, boron oxide, calcium oxide, zinc oxide, by dioxy Aluminium oxide, the silica-titania, silica-zirconium oxide, silica-magnesia, aluminium oxide-two of SiClx cladding Titanium oxide, aluminium oxide-zirconium oxide, zinc aluminate, alumina-boron oxide, silica-boria, aluminum phosphate, aluminate or phosphate, aluminium Phosphate-silicon dioxide, magnesium aluminate, titania-zirconia etc. with and combinations thereof.According in another aspect, solid promoter can The special alkali of department and lewis promoters are born comprising cloth.Cloth, which is born, takes charge of the representative and non-limiting of special alkali and lewis promoters Example may include aluminium oxide, titanium dioxide, zirconium oxide, magnesia, boron oxide, calcium oxide, zinc oxide, by coated with silica Aluminium oxide, silica-titania, silica-zirconium oxide, silica-magnesia, aluminium oxide-titanium dioxide, oxygen Change aluminium-zirconium oxide, zinc aluminate, alumina-boron oxide, silica-boria, aluminum phosphate, aluminate or phosphate, aluminate or phosphate-two Silica, magnesium aluminate, titania-zirconia etc. with and combinations thereof.

Consistent with aspect of the invention, solid promoter may include following (or is substantially made up of or by with the following group At): soild oxide.In general, soild oxide may include oxygen and it is one or more selected from periodic table the 1st, 2,3,4,5,6,7, 8, the element of 9,10,11,12,13,14 or 15 races, or include oxygen and one or more elements selected from group of the lanthanides or actinides (see, e.g., " Huo Li concise chemical dictionary (Hawley's Condensed Chemical Dictionary) ", the 11st edition, John Wiley&Sons,1995；Cotton, F.A., Wilkinson, G., Murillo, C.A., and Bochmann, M., " Advanced Inorganic Chemistry (Advanced Inorganic Chemistry) ", the 6th edition, Wiley-Interscience, 1999). For example and without being limited thereto, soild oxide may include oxygen and one or more elements selected from the following: Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn, Zr, Na, K, Cs, Ca, Ba and Li。

The illustrative example that can be used as the soild oxide of solid promoter as described herein may include but be not limited to Al₂O₃、B₂O₃、BeO、Bi₂O₃、BaO、MgO、CaO、CdO、Ce₂O₃、Co₃O₄、Cr₂O₃、CuO、Fe₂O₃、Ga₂O₃、K₂O、La₂O₃、 Mn₂O₃、MoO₃、Na₂O、NiO、P₂O₅、Sb₂O₅、SiO₂、SnO₂、SrO、XhO₂、TiO₂、V₂O₅、WO₃、Y₂O₃、ZnO、ZrO₂Deng packet Include its mixed oxide with and combinations thereof.In addition, soild oxide is intended individually or to combine the carbonate for covering the above element And hydroxide.The illustrative and non-limiting example of carbonate includes sodium carbonate, sodium bicarbonate, potassium carbonate, cesium carbonate etc..

On the one hand, soild oxide may include silica, aluminium oxide, titanium dioxide, zirconium oxide, magnesia, boron oxide, Calcium oxide, zinc oxide, silica-alumina, aluminium oxide, silica-titania, titanium dioxide by coated with silica Silicon-zirconium oxide, silica-magnesia, aluminium oxide-titanium dioxide, aluminium oxide-zirconium oxide, zinc aluminate, alumina-boron oxide, Silica-boria, aluminum phosphate, aluminate or phosphate, aluminate or phosphate-silica, magnesium aluminate, titania-zirconia etc., or A combination thereof；Alternatively, silica；Alternatively, aluminium oxide；Alternatively, titanium dioxide；Alternatively, zirconium oxide；Alternatively, magnesia；Alternatively, Boron oxide；Alternatively, calcium oxide；Alternatively, zinc oxide；Alternatively, silica-alumina；Alternatively, by the oxidation of coated with silica Aluminium；Alternatively, silica-titania；Alternatively, silica-zirconium oxide；Alternatively, silica-magnesia；Alternatively, oxidation Aluminium-titanium dioxide；Alternatively, aluminium oxide-zirconium oxide；Alternatively, zinc aluminate；Alternatively, alumina-boron oxide；Alternatively, silica- Boron oxide；Alternatively, aluminum phosphate；Alternatively, aluminate or phosphate；Alternatively, aluminate or phosphate-silica；Alternatively, magnesium aluminate；Alternatively, dioxy Change titania-zirconia.On the other hand, soild oxide may include magnesium aluminate, calcium aluminate, zinc aluminate, zirconium aluminate, sodium aluminate, oxygen Change magnesium zirconium, sodium oxide molybdena zirconium, calcium oxide zirconium, lanthana chromium, barium monoxide titanium etc., or combinations thereof；Alternatively, magnesium aluminate；Alternatively, aluminic acid Calcium；Alternatively, zinc aluminate；Alternatively, zirconium aluminate；Alternatively, sodium aluminate；Alternatively, magnesia zirconium；Alternatively, sodium oxide molybdena zirconium；Alternatively, oxidation Calcium zirconium；Alternatively, lanthana chromium；Alternatively, barium monoxide titanium.Generate the various sides of suitable soild oxide and hybrid solid oxide Method, such as cogelledization, doping or dipping, be disclosed in for example below in: U.S. Patent No. 6,107,230, the 6th, 165,929 Number, No. 6,294,494, No. 6,300,271, No. 6,316,553, No. 6,355,594, No. 6,376,415, the 6th, No. 388,017, No. 6,391,816, No. 6,395,666, No. 6,524,987, No. 6,548,441, the 6,548,442nd Number, No. 6,576,583, No. 6,613,712, No. 6,632,894, No. 6,667,274, No. 6,750,302, the 7th, 294, No. 599, the 7th, 601, No. 665, the 7th, 884, No. 163 and the 8th, 309, No. 485 are incorporated to this in entirety by reference Wen Zhong.Preparation can be used as other appropriate methods of the soild oxide of solid promoter and program is those skilled in the art It is known.

As disclosed herein, soild oxide may include by the aluminium oxide of coated with silica, such as U.S. Patent No. 7, 884, No. 163 (for example, Sasol28 or Sasol40) described in.This kind of oxidation by coated with silica Aluminium solid oxide material is generally rich in aluminium oxide, by the weight of aluminium oxide and silica in the aluminium oxide of coated with silica Amount than (aluminium oxide: silica) usually 1.05:1 to 50:1,1.1:1 to 25:1,1.2:1 to 12:1,1.2:1 to 4:1, In the range of 1.3:1 to 6:1 or 1.3:1 to 3:1.

Consistent with aspect of the invention, solid promoter may include following (or mainly consists of or by with the following group At): clay or column clay.The clay or organic pillared interlayered clay material that solid promoter can be used as in disclosed method can be covered In its native state or the clay materials of wetting, ion exchange, column or the various ion processings of other methods is passed through.One A little aspects, clay or column clay may include and compared with macrocation, including multicore high charge metal complex cation from The clay of son exchange.In other aspects, clay or organic pillared interlayered clay material may include the clay with simple salt ion exchange, including But it is not limited to and the Al of the ligand of such as halide, acetate, sulfate, nitrate or nitrite (III), Fe (II), Fe (III) and the salt of Zn (II).

On the other hand, clay or organic pillared interlayered clay material may include column clay.Term " column clay " for refer to Larger, typically multicore high charge metal complex cationic ion exchange clay material.The example of this kind of ion include but It is not limited to Keggin ion, there can be charge, such as 7+, various multi-metal oxygen acid groups and other larger ions.Therefore, term column Change typically refers to simple switched reaction, and wherein the tradable cation of clay material can be through larger highly charged ion, such as Keggin ion exchange.These polymer cations are then immobilized in clay parting and can be converted to effectively in calcining Ground supports metal oxide " column " of the argillic horizon as pipe column structure.Therefore, it is drying and calcined clay is in clay After generating support column between layer, the lattice structure of expansion can be maintained and porosity can be enhanced.Gained hole can be in shape and ruler Very little aspect changes with column material used and parent clay material and other parameters.The discovery of the example of column and column clay In T.J.Pinnavaia, " 220 (Science 220) of science " (4595), 365-371 (1983)；J.M.Thomas, " insertionization Learn (Intercalation Chemistry) ", (S.Whittington and A.Jacobson are compiled) the 3rd chapter, is learned by the 55-99 pages Art Press, Inc (Academic Press, Inc.), (1972)；U.S. Patent No. 4,452,910；U.S. Patent No. 5, No. 376,611；In U.S. Patent No. 4,060,480；The disclosure of which is incorporated herein by reference in its entirety.

In some respects, clay or column clay may include montmorillonite (montmorillonite), bentonite, nontronite (nontronite), hectorite (hectorite), galapectite (halloysite), vermiculite (vermiculite), mica, fluorine cloud Mother, chlorite (chlorite), sepiolite (sepiolite), attapulgite (attapulgite), magnalium skin stone (palygorskite), illite (illite), saponite (saponite), alumina, montmorillonite, kaolin (kaolinite), leaf Alabaster (pyrophyllite) etc., or any combination thereof.In other aspects, clay or column clay may include montmorillonite；Alternatively, Bentonite；Alternatively, nontronite；Alternatively, hectorite；Alternatively, galapectite；Alternatively, vermiculite；Alternatively, mica；Alternatively, fluormica；Or Person, chlorite；Alternatively, sepiolite；Alternatively, attapulgite；Alternatively, magnalium skin stone；Alternatively, illite；Alternatively, saponite；Alternatively, Alumina；Alternatively, montmorillonite；Alternatively, kaolin；Alternatively, pyrophyllite.

According to an aspect of the present invention, solid promoter may include silica, aluminium oxide, silica-alumina, phosphorus Sour aluminium, alumina-boron oxide, silica-magnesia, silica-titania, zirconium oxide, magnesia, magnesium aluminate, sea Afrodite, titanium dioxide, magnalium skin stone, montmorillonite, talcum, kaolin, galapectite, pyrophyllite etc. with and combinations thereof.According to another Aspect, solid promoter may include silica, aluminium oxide, silica-alumina, aluminum phosphate, alumina-boron oxide, two Silica-magnesias, silica-titania, zirconium oxide, magnesia, magnesium aluminate, titanium dioxide etc. with and combinations thereof.Root According to another aspect, solid promoter may include sepiolite, magnalium skin stone, montmorillonite, talcum, kaolin, galapectite, pyrophyllite etc. With and combinations thereof.According in another aspect, solid promoter may include aluminium oxide, zirconium oxide, magnesia, magnesium aluminate, sepiolite etc. With and combinations thereof；Alternatively, aluminium oxide；Alternatively, zirconium oxide；Alternatively, magnesia；Alternatively, magnesium aluminate；Alternatively, sepiolite.

The solid promoter covered herein can have any suitable surface area, pore volume and granularity, as will be by institute The technical staff in category field identifies.For example, the pore volume of solid promoter can in 0.1mL/g to 2.5mL/g or In the range of 0.5mL/g to 2.5mL/g.On the other hand, the pore volume of promotor can be 1mL/g to 2.5mL/g or 0.1mL/ G to 1.5mL/g.Alternatively, pore volume can be 0.1mL/g to 1.0mL/g or 0.2mL/g to 1.0mL/g.In addition, alternatively, solid The BET surface area of promotor can be in 10m²/ g to 750m²/g；Alternatively, 100m²/ g to 750m²/g；Alternatively, 100m²/ g to 500m²/ g；Alternatively, 30m²/ g to 200m²In the range of/g.On the other hand, the surface area of solid promoter can be 20m²/ g to 500m²/ g、30m²/ g to 350m²/g、100m²/ g to 400m²/g、200m²/ g to 450m²/ g or 150m²/ g to 350m²/g.Solid promotes The average particle size visual method particularity of agent and change significantly, however, generalling use 5 microns to 500 microns, 10 microns to 250 Micron or 25 microns are to the average particle size in 200 micron ranges.Alternatively, 1/8 inch to 1/4 inch of granule or pearl can be used Grain.

Before use, these solid promoters can be calcined.Calcining step can be at various temperature and period and in various atmosphere It encloses and is carried out in (inert atmosphere, oxidation atmosphere, reduction atmosphere).For example, calcining step can be calcined at the peak in following range At a temperature of carry out: 150 DEG C to 1000 DEG C；Alternatively, 250 DEG C to 1000 DEG C；Alternatively, 200 DEG C to 750 DEG C；Alternatively, 200 DEG C to 600 ℃；Alternatively, 250 DEG C to 950 DEG C；Alternatively, 250 DEG C to 750 DEG C；Alternatively, 400 DEG C to 700 DEG C；Alternatively, 300 DEG C to 650 DEG C；Or Person, 400 DEG C to 600 DEG C.In these and other aspects, these temperature ranges are also intended to cover wherein calcining step and are belonging to accordingly Under a series of different temperatures (for example, initial calcination temperature, peak calcination temperature) in range rather than under single fixed temperature The environment of progress.For example, calcining step can start under initial calcination temperature, and then the temperature of calcining step can rise Height arrives peak calcination temperature, for example, the peak calcination temperature in the range of 500 DEG C to 1000 DEG C or 250 DEG C to 750 DEG C.

The duration of calcining step is not limited to any special time period.Therefore, calcining step for example can arrive 15-45 less Minute to the period up to 12-24 hours or in larger scope carries out.Calcination time appropriate visually such as initial/peak calcining Depending on temperature and the atmosphere calcined under it and other parameters.However, in general, calcining step can be carried out in the period, The period can be at 45 minutes to 18 hours, such as 45 minutes to 15 hours, 1 hour to 12 hours, 2 hours to 10 hours, 3 In the range of hour to 10 hours or 4 hours to 10 hours.

According to the present invention, solid promoter may include following (or mainly consists of or be made up of): at The soild oxide of reason.For example, treated soild oxide can be handled for calcining solid oxide, by metal Soild oxide, the soild oxide of chemical modification handled by metal or combinations thereof.Treated soild oxide Soild oxide can be any suitable soild oxide or any soild oxide disclosed herein, such as aluminium oxide, two Silica-alumina, by the aluminium oxide of coated with silica, aluminate or phosphate, sodium carbonate or sodium bicarbonate etc..If necessary Words, more than a kind of combination method for use in the present invention of treated soild oxide.In a particular aspects of the invention, Soild oxide may include aluminium oxide, silica-alumina, by or mixtures thereof aluminium oxide of coated with silica.

Consistent with aspect of the invention, treated soild oxide may be characterized as lewis acid.In addition, alternatively, through The soild oxide for crossing processing may be characterized as cloth and bear the special alkali of department.Therefore, in some respects, treated soild oxide can table Sign is that cloth bears department special both alkali and lewis acid.

As disclosed herein, treated soild oxide can be calcining solid oxide.In general, in present invention side Before the step of method (1) or step (I), treated soild oxide can be by any suitable temperature or herein It is disclosed it is any at a temperature in the range of calcine and formed.Usually can be used 150 DEG C to 1000 DEG C, 200 DEG C to 750 DEG C or Calcination temperature in the range of 200 DEG C to 600 DEG C.Treated soild oxide in this aspect of the invention is said Bright property and non-limiting example may include calcining sodium carbonate, calcining sodium bicarbonate, calcining potassium carbonate, calcining cesium carbonate, calcining oxygen Change aluminium, calcined zirconia, calcined magnesia etc. with and combinations thereof.

As disclosed herein, treated soild oxide can be the soild oxide handled by metal.Term " being handled by metal " soild oxide intend to cover alternatively be described as oxide containing metal solid, metal impregnation is consolidated One of soild oxide of oxide body, metal-modified soild oxide and/or metal enrichment or a variety of solid oxygen Compound.In general, can pass through before (1) or step (I) by the soild oxide that metal is handled the method for the invention the step of Method comprising making any suitable soild oxide contact and calcine with any suitable metal-containing compound generates.Calcining can It is carried out simultaneously and/or after this contact procedure with this contact procedure, and can be under any suitable conditions of or at this It is carried out under any calcination condition disclosed in text.

It may include alkali metal, alkaline-earth metal, transition metal or any combination thereof (example by the soild oxide that metal is handled Such as, transition metal and alkali metal).When the soild oxide by metal processing includes alkali metal, treated solid oxygen Compound can be described as the soild oxide by alkali metal treated, and alkali metal usually individually or with combination includes sodium, potassium or caesium. The illustrative and non-limiting example of soild oxide by alkali metal treated may include the aluminium oxide handled by sodium, pass through The aluminium oxide of potassium processing, the aluminium oxide handled by caesium, by aluminate or phosphate etc. that sodium is handled with and combinations thereof.When by metal When the soild oxide of processing includes alkaline-earth metal, treated soild oxide can be described as consolidating by what alkaline-earth metal was handled Oxide body, and alkaline-earth metal usually individually or with combination includes magnesium, calcium or barium.The solid oxidation handled by alkaline-earth metal The illustrative and non-limiting example of object may include aluminium oxide, by aluminium oxide, the aluminium oxide handled by barium of Calcium treatment etc. With and combinations thereof.When the soild oxide by metal processing includes transition metal, treated soild oxide can claim To pass through the soild oxide that transition metal is handled, and transition metal may include any transition metal disclosed herein, Such as titanium, zirconium, hafnium, tungsten or zinc, and individually or with combination.By the illustrative and non-limit for the soild oxide that transition metal is handled Property example processed may include the aluminium oxide handled by zinc, the aluminium oxide handled by zirconium, by aluminium oxide of sodium-tungsten processing etc. with And combinations thereof.

As disclosed herein, treated soild oxide can be the solid oxygen of the chemical modification handled by metal Compound.In general, the method for the present invention the step of before (1) or step (I), by the solid oxidation for the chemical modification that metal is handled Object can be generated by a kind of method, and the method includes to make any suitable soild oxide and any electrophilic anion contact And (while and/or then) calcine to form the soild oxide of chemical modification, and then make the solid oxygen of chemical modification Compound is contacted with any suitable metal-containing compound.Optionally, another calcining step can be used.

By metal handle chemical modification soild oxide may include alkali metal, alkaline-earth metal, transition metal or its Any combination (for example, transition metal and alkali metal).When the soild oxide of the chemical modification by metal processing includes alkali gold When category, treated soild oxide can be described as the soild oxide of the chemical modification by alkali metal treated, and alkali gold Belong to and usually individually or with combination includes sodium, potassium or caesium.When the soild oxide of the chemical modification by metal processing includes alkaline earth When metal, treated soild oxide can be described as the soild oxide of the chemical modification handled by alkaline-earth metal, and Alkaline-earth metal usually individually or with combination includes magnesium, calcium or barium.When the soild oxide packet of the chemical modification by metal processing When containing transition metal, treated soild oxide can be described as the solid oxidation of the chemical modification handled by transition metal Object, and transition metal may include any transition metal disclosed herein, such as titanium, zirconium, hafnium, tungsten or zinc, and individually or With combination.The illustrative and non-limiting example of the soild oxide of the chemical modification handled by metal may include by sodium The chlorinated aluminas of reason, the sulfated alumina handled by sodium, the sulphation that is handled by sodium by coated with silica Aluminium oxide, by sodium handle it is fluorinated by the aluminium oxide of coated with silica, by sodium handle fluorinated silica-oxidation Aluminium, by sodium handle fluorination-chlorination by aluminium oxide of coated with silica etc. with and combinations thereof.

When it is present, the soild oxide by metal processing or the soild oxide of the chemical modification by metal processing In any metal usually at least amount of 0.5 weight % or at least 1 weight % presence.For example, it is handled by by metal Soild oxide (or by metal processing chemical modification soild oxide) poidometer, by metal handle solid Metal of the oxide (soild oxide of the chemical modification handled by metal) usually containing 1 to 30 weight %.Herein Provided in particular aspects, by by metal processing soild oxide (or by metal processing chemical modification solid Oxide) total weight, by metal handle soild oxide (or by metal processing chemical modification solid oxidation Object) 1 to 25 weight %, 2 to 30 weight %, 2 to 25 weight %, 5 to 30 weight %, 5 to 25 weight %, 3 to 15 weights can be contained Measure the metal of %, 5 to the 12 weight weight of % or 6 to 18 %.

In method herein disclosed, the soild oxide of any suitable chemical modification can be used for the present invention, nothing By the mixture or combination of the soild oxide for being chemical modification or the soild oxide of two or more different chemical modifications. The soild oxide of chemical modification may include the soild oxide with electrophilic anion contact, for example, disclosed herein Any soild oxide and any electrophilic anion.On the one hand, the soild oxide of chemical modification may include and electrophilic The soild oxide of anion contact, the soild oxide contain Lewis acidic metal ion.Suitable chemical modification The non-limiting example of soild oxide is disclosed in such as U.S. Patent No. 7,294,599, No. 7,601,665, the 7th, In 884, No. 163, the 8th, 309, No. 485, the 8th, 623, No. 973, the 8th, 703, No. 886 and the 9th, 023, No. 959, with full text The mode of reference is incorporated herein.

For handle or the electrophilic component of modified solid oxide can for after treatment increase soild oxide Louis Any component of this or bronsted acidity (compared to the soild oxide of unused at least one electrophilic anionic treatments).Root According on one side, electrophilic component can be for derived from salt, acid or the (volatilization as being used as source of anions or precursor of other compounds Property organic compound) electrophilic anion.The example of electrophilic anion may include but be not limited to sulfate radical, bisulfate ion, Fluorine ion, chloride ion, bromide ion, iodide ion, fluorosulfuric acid root, fluoboric acid root, phosphate radical, fluorophosphoric acid root, trifluoroacetic acid root, trifluoro Methanesulfonate, fluorine zirconic acid root, fluotitanic acid root, phosphoryl tungstate radicle, tungstate radicle and molybdate, including its mixture and combination.Separately It outside, can also be using other ions or non-ionic compound in the source as these electrophilic anion.Imagine herein Provided some aspects, electrophilic anion can be, or may include fluorine ion, chloride ion, bromide ion, phosphate radical, fluoroform Sulfonate radical, bisulfate ion or sulfate radical or any combination thereof.In other aspects, electrophilic anion may include sulfate radical, sulfuric acid Hydrogen radical, fluorine ion, chloride ion, bromide ion, iodide ion, fluorosulfuric acid root, fluoboric acid root, phosphate radical, fluorophosphoric acid root, trifluoroacetic acid Root, trifluoromethanesulfonic acid root, fluorine zirconic acid root, fluotitanic acid root or combinations thereof.But in other aspects, electrophilic anion may include sulfuric acid Root, fluorine ion, chloride ion or combinations thereof；Alternatively, sulfate radical；Alternatively, fluorine ion and chloride ion；Alternatively, fluorine ion.

Based on the weight of the soild oxide of chemical modification, the soild oxide of chemical modification can usually contain 1 to 30 weights Measure the electrophilic anion of %.Particular aspects provided by herein, by the total weight of the soild oxide of chemical modification, The soild oxide of chemical modification can be arrived containing 1 to 20 weight %, 2 to 20 weight %, 3 to 20 weight %, 2 to 15 weight %, 3 The electrophilic anion of 15 weight %, 3 to 12 weight %, 4 to the 10 weight weight of % or 5 to 9 %.

In one aspect, the soild oxide of chemical modification may include fluorided alumina, chlorinated aluminas, bromination oxidation Aluminium, sulfated alumina, fiuorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, Sulfated silica-alumina, fluorided silica-zircoma, chlorided silica-zirconia, bromided silica-oxygen Change zirconium, sulfated silica-zirconia, fluorided silica-titania, the fluorinated oxidation by coated with silica Aluminium, fluorination-chlorination are by the aluminium oxide of coated with silica, the aluminium oxide or phosphorylation by coated with silica of sulphation By the aluminium oxide of coated with silica and its any mixture or combination.On the other hand, in approach described herein The soild oxide of used chemical modification can be, or may include fluorided solid oxide and/or sulfated solid oxide, Its non-limiting example may include fluorided alumina, sulfated alumina, fiuorided silica-alumina, sulphation titanium dioxide Silicon-aluminium oxide, fluorided silica-zircoma, it is fluorinated by the aluminium oxide of coated with silica, fluorination-chlorination by dioxy SiClx cladding aluminium oxide or sulphation the aluminium oxide by coated with silica with and combinations thereof.It yet still another aspect, chemistry changes The soild oxide of property may include fluorided alumina；Alternatively, chlorinated aluminas；Alternatively, sulfated alumina；Alternatively, fluorination two Silica-alumina；Alternatively, sulfated silica-alumina；Alternatively, fluorided silica-zircoma；Alternatively, chlorination two Silica-zirconia；Alternatively, the aluminium oxide by coated with silica of sulphation；Alternatively, fluorination-chlorination is by silica The aluminium oxide of cladding；Alternatively, the fluorinated aluminium oxide by coated with silica.In some respects, the solid oxidation of chemical modification Object may include fluorided solid oxide, and in other aspects, the soild oxide of chemical modification may include sulfated solid oxidation Object.

Various methods can be used to form the soild oxide for being suitable for the invention chemical modification.Make soild oxide and inhales Method, suitable electrophilic component and the additive amount of electronic components contact, with metal or metal ion (for example, zinc, nickel, vanadium, Titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium or combinations thereof) dipping, various calcination procedures and condition (for example, 150 DEG C to 1000 DEG C, Calcination temperature in the range of 200 DEG C to 750 DEG C or 400 DEG C to 700 DEG C), calcination time is (for example, 1 minute to 24 hours, 5 Minute to the calcination time in the range of 10 hours or 20 minutes to 6 hours), calciner is (for example, calciner, is such as turned round Other methods of kiln, Muffle furnace or fluidized bed and transfer of heat) and atmosphere is calcined (for example, dry or moist calcining atmosphere, oxygen Change calcining atmosphere (such as air or oxygen), reduction calcining atmosphere (such as carbon monoxide or hydrogen) or nonreactive calcining atmosphere (such as Nitrogen or argon gas)) it is disclosed in such as U.S. Patent No. 6,107,230, No. 6,165,929, No. 6,294,494, the 6th, No. 300,271, No. 6,316,553, No. 6,355,594, No. 6,376,415, No. 6,388,017, the 6,391,816th Number, No. 6,395,666, No. 6,524,987, No. 6,548,441, No. 6,548,442, No. 6,576,583, the 6th, No. 613,712, No. 6,632,894, No. 6,667,274, No. 6,750,302, No. 7,294,599, the 7,601,665th Number, in the 7th, 884, No. 163 and the 8th, 309, No. 485, the patent is incorporated herein by reference in its entirety.Preparation chemistry Modified soild oxide is (for example, sulfated alumina, fiuorided silica-alumina and fluorinated by coated with silica Aluminium oxide etc.) other suitable methods and procedures be known to those skilled in the art.

Diluent

Method disclosed herein typically carries out in the presence of a diluent.The mixture of diluent and/or combination can For these methods.Unless specified otherwise herein, otherwise diluent may include it is following, mainly consist of or be made up of: this Any suitable solvent or any solvent disclosed in text.For example, according to an aspect of the present invention, diluent can wrap Containing aprotic solvent.The representative and unrestricted example of aprotic solvent may include tetrahydrofuran (THF), 2,5- Me₂THF, acetone, toluene, chlorobenzene, pyridine, carbon dioxide etc. with and combinations thereof.Diluent may include weak matches according to another aspect, Position or non-coordinating solvent.The representative and unrestricted example of weak coordination or non-coordinating solvent may include toluene, chlorobenzene, stone Wax, halogenated paraffins etc. with and combinations thereof.According to another aspect, diluent may include solvent containing carbonyl, such as ketone, ester, amide etc. With and combinations thereof.The representative and unrestricted example of the solvent containing carbonyl may include acetone, ethyl methyl ketone, acetic acid second Ester, propyl acetate, butyl acetate, isobutyl isobutyrate, methyl lactate, ethyl lactate, N,N-dimethylformamide etc. and its Combination.In another aspect, diluent may include THF, 2,5-Me₂THF, methanol, acetone, toluene, chlorobenzene, pyridine, or combinations thereof； Alternatively, THF；Alternatively, 2,5-Me₂THF；Alternatively, methanol；Alternatively, acetone；Alternatively, toluene；Alternatively, chlorobenzene；Alternatively, pyridine.

On the one hand, diluent may include following (or mainly consists of or be made up of): aromatic hydrocarbon is molten Agent.It can individually or the non-limiting examples of suitable aromatic hydrocarbon solvents in any combination includes benzene,toluene,xylene (including or mixtures thereof ortho-xylene, meta-xylene, paraxylene) and ethylbenzene or combinations thereof；Alternatively, benzene；Alternatively, toluene；Or Person, dimethylbenzene；Alternatively, ethylbenzene.

On the one hand, diluent may include following (or mainly consists of or be made up of): halogenated aromatic hydrocarbon Solvent.It can individually or the non-limiting example of suitable halogenated aromatic hydrocarbon solvent in any combination includes chlorobenzene, two Chlorobenzene and a combination thereof；Alternatively, chlorobenzene；Alternatively, dichloro-benzenes.

On the one hand, diluent may include following (or mainly consists of or be made up of): ether solvents.It can be single The non-limiting example of suitable ether solvents solely or in any combination includes dimethyl ether, diethyl ether, Di Iso Propyl Ether, two N-propyl ether, di-n-butyl ether, diphenyl ether, Methyl ether, methyl tertiary butyl ether(MTBE), dihydrofuran, tetrahydrofuran (THF), 2,5- Me₂THF, 1,2- dimethoxy-ethane, 1,4- dioxanes and a combination thereof；Alternatively, diethyl ether, butyl oxide, THF, 2,5-Me₂THF、 1,2- dimethoxy-ethane, 1,4- dioxanes and a combination thereof；Alternatively, THF；Alternatively, diethyl ether.

Metal lactone and transition metal-ligand complex compound

In general, method disclosed herein uses metal lactone or transition metal-ligand complex compound.Metal lactone or mistake The transition metal for crossing metal-ligand complex can be the 3rd race to the 8th group 4 transition metal, alternatively, the 8th race to the 11st race transition gold Belong to.In one aspect, for example, transition metal can be Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt or Au, and in another party Face, transition metal can be Fe, Ni or Rh.Alternatively, transition metal can be Fe；Alternatively, transition metal can be Co；Alternatively, transition is golden Category can be Ni；Alternatively, transition metal can be Cu；Alternatively, transition metal can be Ru；Alternatively, transition metal can be Rh；Alternatively, mistake Crossing metal can be Pd；Alternatively, transition metal can be Ag；Alternatively, transition metal can be Ir；Alternatively, transition metal can be Pt；Or Person, transition metal can be Au.

The particular aspects covered herein, transition metal can be Ni.Therefore, in these areas, metal lactone can be Nickel lactone, and transition metal-ligand complex compound can be Ni- ligand complex.

The ligand of metal lactone or transition metal-ligand complex compound can for any suitable neutral electron donor group and/ Or lewis base.For example, suitable neutral ligand may include Sigma's donor solvent, can be coordinated containing one or more To the coordination atom of the transition metal of metal lactone (or transition metal-ligand complex compound).Suitable coordination atom in ligand Example may include but be not limited to O, N, S and P or the combination of these atoms.In some aspects consistent with the present invention, ligand can For bidentate ligand.

The ligand for being used to form metal lactone or transition metal-ligand complex compound on the one hand can be ether, organic carbonyl, sulphur Ether, amine, nitrile or phosphine.On the other hand, it can be acyclic for being used to form the ligand of metal lactone or transition metal-ligand complex compound Ether, cyclic ethers, acyclic organic carbonyl, cyclic annular organic carbonyl, acyclic thioether, epithio ether, nitrile, non-cyclammonium, cyclammonium, acyclic phosphine or ring Phosphine.

Suitable ether may include but be not limited to dimethyl ether, diethyl ether, dipropyl ether, butyl oxide, Methyl ether, methyl propyl ether, Methylbutyl ether, diphenyl ether, benzyl ether, tetrahydrofuran, 2- methyltetrahydrofuran, 2,5- dimethyl-tetrahydrofuran, 2,3- dihydro Furans, 2,5- dihydrofuran, furans, benzofuran, isobenzofuran, dibenzofurans, oxinane, 3,4- dihydro -2H- pyrrole It mutters, 3,6- dihydro -2H- pyrans, 2H- pyrans, 4H- pyrans, 1,3- dioxanes, Isosorbide-5-Nitrae-dioxanes, morpholine etc., including it is substituted Derivative.

Suitable organic carbonyl can include ketone, aldehyde, ester and amide individually or with combination, and illustrative example may include but It is not limited to acetone, acetophenone, benzophenone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, methyl acetate, acetic acid second Ester etc., the derivative being substituted including it.

Suitable thioether may include but be not limited to dimethyl sulfide, diethyl thioether, dipropyl thioether, butyl sulfide, Methyl ethyl sulfide, methyl-propyl thioether, methyl butyl sulfide, diphenylsulfide, xylyl thioether, thiophene, benzothiophene, Thiophane, thiophene alkane etc., the derivative being substituted including it.

Suitable nitrile may include but be not limited to acetonitrile, propionitrile, butyronitrile, benzonitrile, 4- methyl benzonitrile etc., including it is through taking The derivative in generation.

Suitable amine may include but be not limited to methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, di-n-propylamine, two fourths Amine, trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, aniline, diphenylamines, triphenylamine, toluidines, dimethylaniline, dimethylaniline, pyrrole Pyridine, quinoline, pyrroles, indoles, 2- picoline, 3- picoline, 4- picoline, 2,5- dimethyl pyrrole, 2,5- diethyl Pyrroles, 2,5- dipropyl pyrroles, 2,5- dibutyl pyrroles, 2,4- dimethyl pyrrole, 2,4- diethyl pyrroles, 2,4- dipropyl pyrrole It coughs up, 2,4- dibutyl pyrroles, 3,4- dimethyl pyrrole, 3,4- diethyl pyrroles, 3,4- dipropyl pyrroles, 3,4- dibutyl pyrrole It coughs up, 2- methylpyrrole, 2- N-ethyl pyrrole N, 2- propyl pyrrole, 2- butyl pyrroles, 3- methylpyrrole, 3- N-ethyl pyrrole N, 3- propyl pyrrole It coughs up, 3- butyl pyrroles, 3- ethyl -2,4- dimethyl pyrrole, 2,3,4,5- tetramethyl pyrroles, 2,3,4,5- tetraethyl pyrroles, 2, 2'- bipyridyl, 11-7- alkene of 1,8- diazabicyclo [5.4.0], two (2- pyridyl group) dimethylsilanes, N, N, N', N'- tetra- Methyl ethylenediamine, 1,10- phenanthroline, 2,9- dimethyl -1,10- phenanthroline, glyoxal-bis (2,4,6- trimethylphenyl) -1,2- Diimine etc., the derivative being substituted including it.Suitable amine can be primary amine, secondary amine or tertiary amine.

Suitable phosphine and other phosphorus compounds may include but be not limited to trimethyl-phosphine, triethyl phosphine, tripropyl phosphine, tributyl Phosphine, Phenylphosphine, tolylphosphine, diphenylphosphine, xylyl phosphine, triphenylphosphine, trimethylphenyl phosphine, methyldiphenyl base phosphine, diformazan Base Phenylphosphine, ethyldiphenylphosphine, diethyl phenyl phosphine, tricyclohexyl phosphine, Trimethyl phosphite, triethyl phosphite, phosphorous Sour three propyl ester, three cyclohexyl of triisopropyl phosphite, tributyl phosphite and phosphorous acid, 2- (di-t-butyl phosphino-) xenyl, 2- di-t-butyl phosphino- -1,1'- dinaphthalene, triisopropyl -1 2- (di-t-butyl phosphino-) -3,6- dimethoxy -2', 4', 6'-, 1'- xenyl, 2- di-t-butyl phosphino- -2'- methyl biphenyl, 2- (di-t-butyl phosphinomethyl) pyridine, 2- di-t-butyl Phosphino- -2', 4', 6'- triisopropyl -1,1'- xenyl, 2- (dicyclohexyl phosphino-) xenyl, (S)-(+)-(3,5- dioxy Miscellaneous -4- phospha-cycloheptyl [2,1-a；3,4-a'] dinaphthyl -4- base) dimethylamine, 2- (diphenylphosphino) -2'- methoxyl group -1,1'- connection Naphthalene, 1,2,3,4,5- five phenyl -1'- (di-t-butyl phosphino-) ferrocene, bis- (the diphenylphosphino) -1,1'- dinaphthalenes of 2,2'- (BINAP), bis- (dimethyl phosphino-) ethane of 1,2-, bis- (diethylphosphino) ethane of 1,2-, bis- (dipropyl the phosphino-)-second of 1,2- Bis- (diisopropyl phosphino-) ethane of alkane, 1,2-, bis- (dibutyl-phosphino-) ethane of 1,2-, bis- (di-t-butyl-phosphino-) second of 1,2- Bis- (dicyclohexyl phosphino-) ethane of alkane, 1,2-, bis- (dicyclohexyl phosphino-) propane of 1,3-, bis- (the diisopropyl phosphino-s) third of 1,3- Bis- (di-t-butyl phosphino-) propane of bis- (diphenylphosphino) propane of alkane, 1,3-, 1,3-, bis- (diisopropyl phosphino-) butane of 1,4-, Bis- [bis- (3,5- 3,5-dimethylphenyl) phosphino-s] -4,4' of bis- (diphenylphosphino) butane of 1,4-, 2,2'-, 6,6'- tetramethoxy biphenyl Bis- (di-t-butyl phosphinomethyl) pyridines of base, 2,6-, bis- (dicyclohexyl the phosphino-) -1,1'- xenyls of 2,2'-, bis- (bis- rings of 2- Hexyl phosphino- phenyl) ether, the bis- two -1,3- benzodioxoles of (diphenylphosphino) -4,4'- of 5,5'-, 2- tert. butylphosphino Picoline, bis- (diphenylphosphino) ferrocene, bis- (diphenylphosphino) methane, bis- (dicyclohexyl phosphino-) methane, bis- (two- Tert. butylphosphino) methane etc., the derivative being substituted including it.

In other aspects, it is used to form metal lactone or transition metal-ligand complex compound can be carbene, such as N- heterocycle carbon Alkene (NHC) compound.The representative and unrestricted example of suitable N- heterocyclic carbene (NHC) material include the following:

The illustrative and unrestricted reality of applicable metal lactone complex compound (representative nickel lactone) as described herein Example include following compound (Cy=cyclohexyl,^tBu=tert-butyl):

Transition metal-ligand complex compound corresponding with illustrative metal lactone presented below:

Metal lactone (can use nickel as transition metal explanation according to following general reaction process；Ni(COD)₂For bis- (1,5- Cyclo-octadiene) nickel (0)):

And other suitable program synthesis according to known to those skilled in the art.

Suitable ligand, transition metal-ligand complex compound and metal lactone be not limited only to it is disclosed herein those Ligand, transition metal-ligand complex compound and metal lactone.Other suitable ligands, transition metal-ligand complex compound and/or gold During category lactone is described in below for example: U.S. Patent No. 7,250,510, No. 8,642,803 and No. 8,697,909；WO 2015/173276；WO 2015/173277；" organometallic chemistry periodical (Journal of Organometallic Chemistry)",1983,251,C51-C53；Z.Anorg.Allg.Chem.,1989,577,111-114；" organometallic Term prints ", 2004,689,2952-2962；" organo-metallic compound (Organometallics) ", volume 2004,23, 5252-5259；" chemical communication (Chem.Commun) ", 2006,2510-2512；" organo-metallic compound ", the 2010, the 29th Volume, 2199-2202；" Europe chemistry (Chem.Eur.J.) ", 2012,18,14017-14025；" organo-metallic compound ", 2013,32(7),2152-2159；" Europe chemistry ", volume 2014,20,11,3205-3211；The disclosure of which to draw in full Mode is incorporated herein.

Generate alpha, beta-unsaturated carboxylic acid and its salt

In general, independently describing method disclosed herein (for example, metal lactone, diluent, solid promoter (example Such as, treated soild oxide), α, beta-unsaturated carboxylic acid or its salt, transition metal-ligand complex compound, alkene and at it Lower formation α, beta-unsaturated carboxylic acid or the condition of its salt etc.) feature, and can be merged with any combination these features with into The disclosed method of one step description.

According to an aspect of the present invention, the open method for carrying out metal lactone elimination reaction.This method may include with Under (or mainly consist of or be made up of):

(1) make following contact

(a) metal lactone；

(b) diluent；With

(c) solid promoter (for example, treated soild oxide)；And

(2) alpha, beta-unsaturated carboxylic acid or its salt are formed.

Suitable metal lactone, diluent and solid promoter (for example, treated soild oxide) disclosed above. In this method for carrying out metal lactone elimination reaction, for example, at least part diluent may include α, beta-unsaturated carboxylic acid Or its salt, it is formed in (2) this method the step of.

According to another aspect of the present invention, open to generate α, the method for beta-unsaturated carboxylic acid or its salt.This method can wrap Containing following (or mainly consist of or be made up of):

(1) make following contact

(a) metal lactone；

(b) diluent；With

(c) solid promoter (for example, treated soild oxide)；

In generation α, in this method of beta-unsaturated carboxylic acid or its salt, for example, at least part includes metal lactone The diluent of transition metal can be removed this method the step of after (2) and before step (3).It is disclosed above suitable Metal lactone, diluent and solid promoter (for example, treated soild oxide).

In some respects, contact procedure-step (1) of these methods may include making metal lactone, dilution in any order Agent and solid promoter (for example, treated soild oxide) and additional unlisted material.In other sides Face, contact procedure can be mainly consisted of or be made up of: metal lactone, diluent and solid promoter (for example, through Cross the soild oxide of processing) component.Equally, additional material or feature can be used for the step of middle these methods of formation-step (2), α and/or for handling is generated, the step of the method for beta-unsaturated carboxylic acid or its salt-step (3).Furthermore, it is contemplated that carry out gold Belong to lactone elimination reaction and generate alpha, beta-unsaturated carboxylic acid or its salt these methods can be used more than a kind of metal lactone and/or More than a kind of solid promoter (for example, mixture of two kinds of treated soild oxides).In addition, if needing, can adopt Mixture or combination with two or more diluents.

Any suitable reactor, vessel or container can be used for contacting metal lactone, diluent and solid promoter (example Such as, treated soild oxide), the non-limiting example of the reactor, container or container may include flow reactor, Flow reactor, fixed bed reactors and stirred tank reactor, including the reactor more than a serial or parallel connection, and including Any combination of type of reactor and configuration.In particular aspects consistent with the present invention, metal lactone and diluent contact solid The fixed bed of promotor (for example, treated soild oxide), for example, in suitable vessel, such as in continuous fixed bed In reactor.In other aspects, the combination more than a kind of solid promoter, such as the first treated soild oxide can be used It is treated solid with the mixed bed of the second treated soild oxide, the first treated soild oxide and second The sequence bed of oxide body.In these and other aspects, feeding flow, which can face upward or downward, flows through fixed bed.For example, metal Lactone and diluent flowing positioning and reversely can contact the first treated solid oxidation downward with flowing positioning upward Object and subsequent second treated soild oxide.In different aspect, metal lactone and solid promoter (for example, by The soild oxide of processing) it can be by diluent, for example in suitable vessel, such as mixed or stirring in stirred tank reactor And it contacts.

Generate α, the step of the method for beta-unsaturated carboxylic acid or its salt (2) narration formed be adsorbed onto solid promoter (for example, Treated soild oxide) on alpha, beta-unsaturated carboxylic acid addition product.This addition product can contain all or part of α, beta-unsaturated carboxylic acid, and including α, the salt of beta-unsaturated carboxylic acid.

Generating α, the step of the method for beta-unsaturated carboxylic acid or its salt in (3), processing is adsorbed onto solid promoter (example Such as, treated soild oxide) on addition product to generate α, beta-unsaturated carboxylic acid or its salt.Various methods can be used for from Release or desorption α, beta-unsaturated carboxylic acid or its salt in solid promoter (for example, treated soild oxide).At one Aspect, for example, processing step may include the addition for making to be adsorbed on solid promoter (for example, treated soild oxide) Object is contacted with acid.The representative and unrestricted example of suitable acid may include HCl, acetic acid, sodium bisulfate etc. and its Combination.On the other hand, processing step may include making to be adsorbed on solid promoter (for example, treated soild oxide) Addition product contacted with alkali.The representative and unrestricted example of suitable alkali may include carbonate (for example, Na₂CO₃、 Cs₂CO₃、MgCO₃), hydroxide is (for example, Mg (OH)₂, Na (OH)), alkoxide is (for example, Al (OⁱPr)₃、Na(O^tBu)、Mg (OEt)₂) etc. with and combinations thereof (ⁱPr=isopropyl,^tBu=tert-butyl, Et=ethyl).It yet still another aspect, processing step can wrap Containing contacting the addition product being adsorbed on solid promoter (for example, treated soild oxide) with suitable solvent.It closes The representative and unrestricted example of suitable solvent may include solvent containing carbonyl, if ketone, ester or amide are (for example, as above Described in, acetone, ethyl acetate or n,N-Dimethylformamide), alcoholic solvent, water etc. with and combinations thereof.In another aspect, processing Step may include that the addition product being adsorbed on solid promoter (for example, treated soild oxide) is heated to any conjunction Suitable temperature.This temperature can be in such as 50 DEG C to 1000 DEG C, 100 DEG C to 800 DEG C, 150 DEG C to 600 DEG C, 250 DEG C to 1000 DEG C, in the range of 250 DEG C to 550 DEG C or 150 DEG C to 500 DEG C.When the duration of this heating steps is not limited to any specific Between section, as period long enough with from solid promoter (for example, treated soild oxide) discharge α, β-unsaturation Carboxylic acid.Such as skilled artisan recognize that, processing step appropriate is depending on several factors, as the method Specific diluent and for the method particular solid promotor (for example, treated soild oxide) and other examine Worry factor.

It is carrying out metal lactone elimination reaction and is generating α, in these methods of beta-unsaturated carboxylic acid (or its salt), additionally Method and step can be described herein any one of step before, during and/or after carry out.As an example, These methods, which can further include, makes transition metal-ligand complex compound and alkene and carbon dioxide (CO₂) contact to form metal The step of lactone (for example, before step (1)).Above description transition metal-ligand complex compound.Suitably alkene is illustrative With non-limiting example may include ethylene, propylene, butylene (for example, 1- butylene), amylene, hexene (for example, 1- hexene), heptane, Octene (for example, 1- octene), styrene etc. with and combinations thereof.

But it is according to another aspect of the present invention, open to generate α, the method for beta-unsaturated carboxylic acid or its salt.This method can Include following (or mainly consist of or be made up of):

(I) make following contact

(i) transition metal-ligand complex compound；

(ii) alkene；

(iii) carbon dioxide (CO₂)；

(iv) diluent；With

(v) solid promoter (for example, treated soild oxide)；And

(II) alpha, beta-unsaturated carboxylic acid or its described salt are formed.

Suitable transition metal-ligand, alkene, diluent and solid promoter disclosed above are (for example, treated solid Oxide body).In some respects, contact procedure-step (I) of this method can include matching transition metal-in any order It body, alkene, diluent, solid promoter (for example, treated soild oxide) and carbon dioxide and additional does not arrange Material out.In other aspects, contact procedure can be mainly consisted of or is made up of: be made in any order Cross metal-ligand, alkene, diluent, solid promoter (for example, treated soild oxide) and carbon dioxide exposure. Equally, additional material or feature can be used to form the step of this method-step (II).Furthermore, it is contemplated that generate α, β-insatiable hunger It can be used with this of carboxylic acid or its salt method more than a kind of transition metal-ligand complex compound and/or promote more than a kind of solid Agent (for example, mixture of two kinds of treated soild oxides) and/or be more than a kind of alkene.It is also possible to use two kinds or The mixture of more kinds of diluents or combination.As above, whether or not using solid promoter (for example, treated solid oxygen Compound) fixed bed, contact (or mixing) stirred tank or some other reactor configurations and method, any suitable reaction Device, vessel or container can be used for contacting transition metal-ligand, alkene, diluent, solid promoter (for example, treated solid Oxide body) and carbon dioxide.It is presented below that this method is proposed and illustrated although being not intended to be combined with following theory Property reaction process (although not limited to this, but R be H, Na or K):

Independently, (that is, progress metal lactone elimination reaction, generation α, beta-unsaturated carboxylic acid or its salt) institute's public affairs herein The contact of any one of the method opened and forming step can carry out under various temperature, pressure and period.For example, it walks Suddenly the temperature that the temperature that the component in (1) or step (I) contacts first can be identical to or carry out different from forming step.As saying Bright property example, in contact procedure, component can be contacted at temperature T1 first, also, after this initial merging, temperature can It is increased to the temperature T2 for being used to form step (for example, to form α, beta-unsaturated carboxylic acid or its salt).Equally, pressure can connect It touches step and forming step aspect is different.In general, the period in contact procedure can be described as time of contact, in two forming step Period can be described as the reaction time.Time of contact and reaction time can be and be usually different.

On the one hand, the contact procedure of method disclosed herein and/or forming step can be at 0 DEG C to 250 DEG C；Or Person, 20 DEG C to 200 DEG C；Alternatively, 0 DEG C to 95 DEG C；Alternatively, 10 DEG C to 75 DEG C；Alternatively, 10 DEG C to 50 DEG C；Alternatively, 15 DEG C to 70 DEG C In the range of at a temperature of carry out.In these and other aspects, after the initial contact, if it is desired, temperature can be changed into In another temperature of forming step.These temperature ranges, which are also intended to cover wherein contact procedure and/or forming step, to be belonged to The environment for carrying out under a series of different temperatures in respective range rather than being carried out under single fixed temperature.

On the one hand, the contact procedure of method disclosed herein and/or forming step can 5 to 10,000psig, Such as it is carried out under the pressure in the range of 5 to 2500psig.In some respects, pressure can arrive 500psig 5；25 arrive 3000psig；45 arrive 1000psig；Alternatively, in the range of 50 to 250psig.

The contact procedure of the method is not limited to any specific duration.That is, respective components can first quickly or through compared with Long period contacts before initially forming step.Therefore, contact procedure for example can arrive 1-30 seconds to up to 1-12 hours less Or more in the range of period in carry out.In discontinuous or intermittently operated, when being used to form the reaction appropriate of step Between can be depending on the ratio of respective components in such as reaction temperature, reaction pressure and contact procedure and other parameters.In general, so And forming step can carry out certain period of time, the period can be 1 minute to 96 hours, such as 2 minutes to 96 hours, 5 points Clock is in the range of 72 hours, 10 minutes to 72 hours or 15 minutes to 48 hours.

If used method is continuation method, metal lactone/solid promoter catalyst contact/reaction time (or transition metal-ligand/solid promoter catalyst contact/reaction time) can be according to weight space velocity per hour (WHSV)-per unit time the weight of metal lactone (or transition metal-ligand complex compound) ratio expression, the metal lactone It is contacted with the solid promoter (for example, treated soild oxide) of given weight.Although not limited to this, promote by solid Into the meter of agent (for example, treated soild oxide), used WHSV can be 0.05 to 100,0.05 to 50,0.075 To in the range of 50,0.1 to 25,0.5 to 10,1 to 25 or 1 to 5.

In method herein disclosed, based on metal lactone (or the transition metal by transition metal-ligand complex compound Meter), α, beta-unsaturated carboxylic acid or its salt) molar yield be at least 2%, and more generally can be at least 5%, at least 10% or at least 1.5%.In certain aspects of the present disclosure, molar yield can be at least 25%, at least 50%, at least 75%, extremely Few 100%, at least 125%, at least 150%, at least 200% or at least 350%, and usually can up to 10,000% or 100,000% or 1,000, in the range of 000%, as realizing catalytic efficiency.

The specific alpha, beta-unsaturated carboxylic acid (or its salt) that method of the invention can be used to be formed or generated is not particularly limited. The illustrative and non-limiting example of alpha, beta-unsaturated carboxylic acid may include acrylic acid, methacrylic acid, 2- ethylacrylic acid, cortex cinnamomi Acid it is equal with and combinations thereof.The illustrative and non-limiting example of the salt of alpha, beta-unsaturated carboxylic acid may include sodium acrylate, acrylic acid Magnesium, Sodium methacrylate etc. with and combinations thereof.

Once being formed, then suitable technology can be used to purify and/or separate for α, beta-unsaturated carboxylic acid (or its salt) (isolate/separate), the technology may include but be not limited to evaporation, distillation, chromatography, crystallization, extraction, washing, decantation, Filtering, dry etc., the combination including being more than these a kind of technologies.On the one hand, carry out metal lactone elimination reaction method (or Generate α, the method for beta-unsaturated carboxylic acid or its salt) it can further include from other components, such as diluent and/or solid promoter (separate/isolate) α, the step of beta-unsaturated carboxylic acid (or its salt) are separated in (for example, treated soild oxide) Suddenly.For example, solid- liquid separation technology can be used.

Example

Further illustrate that the present invention, the example should not be interpreted as in any way to model of the invention by following instance Enclose application limitation.In the case where not departing from spirit or the scope of the appended claims of the invention, retouching for this paper is being read After stating, one of ordinary skill in the art can associate various other aspects, modification and its equivalent.

In following certain examples, CO can be derived from₂The following nickel lactone complex compound of ethylene coupling is various equal for assessing Uniform isomery (solid) promotor.

General nickel lactone elimination reaction carries out as follows.Flask is packed into 10mg nickel lactone (A, B or C), promotor and about 10mL diluent.In being vigorously stirred lower heating reaction mixture in oil bath under conditions of describing in the following example.Make to react Mixture is cooled to environment temperature, is then acidified.Relative to internal standard sorbic acid stock solution, pass through D₆In acetone¹H NMR is surveyed Determine the yield of acrylic acid.

Example 1-8

The assessment that uniform activation agent/promotor-acrylate is eliminated

For example 1-8, it is small that 5 equivalent activators/promotor (every Ni) cultivates 3 with nickel lactone (A, B or C) at 50 DEG C When, later final sour water solution and extract with by be directed to interior target¹H NMR quantifies the amount of acrylic acid, such as in following reaction stream It is reflected in journey:

Uniform activation agent/promotor assessment result is summarized in Table I.Diluent difference used in example 1 and example 2-7 For 5:1 tetrahydrofuran/acetone and tetrahydrofuran.Example 8 is studied in tetrahydrofuran, methanol and acetone.The uniform promotion of example 5 Agent be solution of the methylaluminoxane in toluene, and the uniform promotor of example 6 be Mg (ⁿBu)₂With the mixture of methanol, produce Raw alkoxide.As shown in Table I, uniform activation agent/promotor of example 1-8, which fails to generate, has any studied nickel lactone In any acrylic acid.

The molar yield of Table I example 1-8

Remarks: Me=methyl；ⁱPr=isopropyl；ⁿBu=normal-butyl.

Example 9-12

The assessment that solid/isomery activator/promotor-acrylate is eliminated

Example 9-12 is carried out in a manner of being similar to example 2-7, and (every 25 equivalent of Ni is reflected such as in following reaction process Based on solid activating agent/promotor site concentration (mmol/g)；HCl is used to discharge the acrylic acid for analysis):

Solid/isomery activator/promotor (calcining at 400 DEG C) assessment result is summarized in Table II.Unexpectedly Ground, with example 2-3,5-6 and 8 uniform Al and Mg promotor in contrast, the solid promoter of example 9-12, which generates, can measure The acrylic acid of amount.More surprisingly, example 11A and 11C (zirconium oxide) and example 12A and 12C (magnesia) provide acrylic acid Significant molar yield (20% to 90%).

The molar yield of Table II example 9-12

Example 13-24

The assessment that solid/isomery activator/promotor-acrylate is eliminated

Example 13-24 is carried out in a manner of being similar to example 9-12, only has nickel lactone A, such as in following reaction process (every 25 equivalent of Ni is based on solid activating agent/promotor site concentration (mmol/g) for reflection；HCl is used to discharge for analysis Acrylic acid):

Solid/isomery activator/promotor (calcining at 400 DEG C) assessment result in different diluent/solvents is general It is set forth in Table III.Unexpectedly, aluminium oxide, zirconium oxide, magnesia, magnesium aluminate and sepiolite are generated using different diluents A large amount of acrylic acid, molar yield are usually 5% to 90%.

Magnesium aluminate is further tested under different calcination conditions.At 400 DEG C in THF diluent, yield is 37%.Yield is reduced to 6% by the calcining at 250 DEG C, and yield is increased to 47% by the calcining at 550 DEG C.

Example 25-33

The assessment that treated soild oxide-acrylate is eliminated

Example 25-33 by mixing 18 μm of ol nickel compounds, 18 μm of ol diphosphine ligands, 5mL diluent (THF or toluene) and Treated soild oxide (example 25-30 200mg being directed to, for example 31-33 50mg) carries out 30 at 60 DEG C and arrives It 60 minutes, is such as reflected in following reaction process:

Sulfuric acid hydrogen sodium is used to discharge the acrylic acid for analysis, extracts into D later₂O/ acetone-d₆With by relative to Internal sorbic acid standard¹H NMR spectra quantifies the amount of acrylic acid.

The pore volume of the aluminium oxide of base material that is used and being used as example 25-29,34-37,39 and 41 in example 30 For 1.3mL/g, surface area 330m²/g.For example 30, aluminium oxide is calcined 3 hours in dry air at 500 DEG C.

The aluminium oxide of example 25 handled by zinc contains the aqueous of 2.5g zinc chloride with 30mL by mixing 10g aluminium oxide Solution preparation.Go to remove water in vacuum drying oven at 90 DEG C it is overnight after, dried powder calcines three at 500 DEG C in dry air Hour.Example 27 and 29 is similarly prepared by the aluminium oxide of Calcium treatment, but calcining carries out in dry air at 600 DEG C 3 hours.

The chlorinated aluminas of example 26 passes through time of the warp less than 1 minute for 3mL CCl₄Liquid (and the CCl that gasifies₄) note It is mapped in three hours nitrogen streams of calcined alumina, generating chlorinated aluminas at 500 DEG C and preparing.

The aluminium oxide of example 28 handled by sodium contains 4.6g sodium bicarbonate by mixing 22.8g aluminium oxide and 60mL Aqueous solution preparation.Go to remove water in vacuum drying oven at 90 DEG C it is overnight after, dried powder is forged in dry air at 200 DEG C It burns three hours.

In example 31 and example 32, calcining 6 is small in dry air at 200 DEG C respectively for sodium bicarbonate and cesium carbonate When, and in example 33, do not calcine and (do not handle) sodium carbonate.

The treated soild oxide of example 25-33 and the assessment result of untreated sodium carbonate are summarized in Table IV In.Unexpectedly, in contrast with the chlorinated aluminas of example 26, the treated solid oxidation of example 25 and 27-30 Object generates a large amount of acrylic acid, and molar yield is in the range of about 3% to 27%.Also unexpectedly, the calcining of example 31-32 Carbonate generates acrylic acid, and the example 33 without calcining does not generate acrylic acid.

Example 34-41

Treated soild oxide-is by CO₂The assessment of acrylate is converted into ethylene

Example 34-41 in the reactor for being with 150psig ethylene, later 300psig carbon dioxide balance by mixing 0.1mmol nickel compound, 0.11mmol diphosphine ligand, 500mL diluent and the treated soild oxide of 1g, and then It is heated to 100 DEG C to carry out up to 6 hours, such as be reflected in following reaction process:

Reaction product is extracted into D₂O/ acetone-d₆For by relative to internal sorbic acid standard¹HNMR spectrum The measurement of acrylate yield.

Example 34 by sodium handle sulfated alumina by the solution of mixed aluminium oxides and sulfuric acid in methanol with About 15 weight % sulfuric esters are generated based on the weight of sulfated alumina and are prepared.Drying is overnight under vacuum at 110 DEG C Later, dried powder is calcined three hours in dry air at 600 DEG C.After cooling, by 4.2g sulfated alumina and uncle 2g Sodium butoxide is incorporated in 60mL toluene, forms yellow suspension.It stirs mixture 18 hours at ambient temperature, filtering, and It is washed with 10mL toluene, forms the colorless solid (sulfated alumina handled by sodium) of example 34.

Example 36 by sodium handle chlorinated aluminas use example 26 chlorinated aluminas, and in example 34 It is prepared after identical sodium processing routine used.

The fluorinated aluminium oxide by coated with silica of example 41 is made in aluminium oxide and isopropanol first by preparation Tetraethyl orthosilicate (is equal to 25 weight %SiO₂) contact.After drying, it calcines at 600 DEG C by the oxygen of coated with silica Change aluminium 3 hours.Then, the fluorinated aluminium oxide (7 weight %F) by coated with silica passes through molten with the fluoram in methanol Liquid dipping calcining by the aluminium oxide of coated with silica, drying and then calcine 3 hours and prepare at 600 DEG C.Example The 35 fluorinated aluminium oxide by coated with silica handled by sodium uses the fluorinated by coated with silica of example 41 Aluminium oxide, and prepared after with identical sodium processing routine used in example 34.

The aluminium oxide (8 weight % sulfuric ester) by coated with silica for the sulphation of example 37 handled by sodium uses As in example 41 description preparation by the aluminium oxide of coated with silica and subsequent sulphation and described in example 34 The sodium of mode is handled and is prepared.

The fiuorided silica-alumina of example 38 handled by sodium, which uses, has 13 weight % aluminium oxide, 400m²/g Surface area and 1.2mL/g pore volume silica-alumina as base material.This material with contain ammonium fluoride hydrogen Aqueous solution mixing, drying is overnight under vacuum at 110 DEG C, and calcines three hours in dry air at 450 DEG C. Fiuorided silica-alumina then carries out sodium processing in a manner of identical with described in example 34.

Example 39 by sodium handle tungsten oxide aluminium by first with 6.341g ammonium metatungstate hydrate in 50mL go from Aqueous solution in sub- water makes 12.91g aluminium oxide (surface area 300m², pore volume 1.2mL/g, average particle size is 100 micro- Rice) it is saturated to obtain wetting sand consistency and prepares.After separation and drying solid, calcining solid 3 hours at 600 DEG C.Sodium Processing is carried out in a manner of identical with described in example 34.

The aluminate or phosphate of example 40 handled by sodium is by being added to 1 molar nitric acid aluminium for 100mL deionized water first It in nonahydrate, and heats the mixture to 60 DEG C and prepares, generate uniform supernatant liquid.Then, 0.9mol is added Binary ammonium phosphate, and be dissolved into solution.After stirring 1 hour at 60 DEG C, the ammonium hydroxide of concentration is added until gel Occur, forms hard solid.Solid is broken into compared with fractionlet, and is washed three times in the deionized water of 4L warm.Finally wash It washs and is completed in 4L normal propyl alcohol, filtered later, and is then dry in vacuum drying oven at 110 DEG C.Dried powder then exists It is calcined 3 hours at 600 DEG C, and then carries out sodium processing in a manner of described in example 34.

The assessment result of the treated soild oxide of example 34-41 is summarized in Table V.Unexpectedly, with reality The fluorinated aluminium oxide by coated with silica of example 41 (it does not generate acrylic acid) in contrast, example 34-40 by The soild oxide of reason generates a large amount of acrylic acid, and molar yield is 38% to 181%.Example 34-35's and 37-38 passes through metal The soild oxide of the chemical modification of processing is directly from CO₂It is particularly successful with catalysis generation acrylic acid aspect in ethylene, mole Yield is more than 100% (by the transition metal of transition metal-ligand complex compound).

The molar yield of Table III example 13-24

Table IV example 25-33.

Table V example 34-41.

Example	Treated soild oxide	Diluent	Acrylate molar yield (%)
				34	NaO^tBu sulfated alumina	Toluene	102
35	NaO^tThe fluorinated aluminium oxide by coated with silica of Bu	Toluene	131
				36	NaO^tBu chlorinated aluminas	Toluene	38
37	NaO^tThe aluminium oxide by coated with silica of Bu sulphation	Toluene	181
				38	NaO^tLBu fiuorided silica-alumina	Toluene	118
39	NaO^tBu tungsten oxide aluminium	Toluene	76
				40	NaO^tBu aluminate or phosphate	Toluene	95
41	The fluorinated aluminium oxide by coated with silica	Toluene	0

Above with reference to a large amount of aspects and the specific example description present invention.According to being discussed in detail above, the technology of fields Personnel will associate a variety of versions.All such apparent versions are all expected in the whole of the appended claims In range.Other aspects of the invention may include but be not limited to it is following (aspect is typically described as " including ... ", but substitute Ground, unless specifically stated otherwise, otherwise aspect can " mainly by ... form " or " by ... form "):

A kind of method for carrying out metal lactone elimination reaction of aspect 1., the method includes:

(1) make following contact

(a) metal lactone；

(b) diluent；With

(c) treated soild oxide；And

(2) alpha, beta-unsaturated carboxylic acid or its salt are formed.

Method defined in 2. aspect 1 of aspect, wherein at least a part of diluent are included in the α formed in step (2), Beta-unsaturated carboxylic acid or its salt.

A kind of generation α of aspect 3., the method for beta-unsaturated carboxylic acid or its salt, the method includes:

(1) make following contact

(a) metal lactone；

(b) diluent；With

(c) treated soild oxide；

(2) addition product for the alpha, beta-unsaturated carboxylic acid being adsorbed on the treated soild oxide is formed；And

(3) addition product that processing is adsorbed on the treated soild oxide is to generate the α, β-insatiable hunger With carboxylic acid or its described salt.

Method defined in 4. aspect 3 of aspect, the wherein at least dilution of transition metal of a part comprising metal lactone Agent removes after step (2).

Method defined in any one of 5. aspect 1-4 of aspect, wherein metal lactone and diluent connect in step (1) Touch the fixed bed of treated soild oxide.

Method defined in any one of 6. aspect 1-4 of aspect, wherein in step (1), metal lactone and process processing Soild oxide contacted by the mixed/stirred in diluent.

Method defined in any one of 7. aspect 3-6 of aspect, wherein processing step is treated comprising making to be adsorbed onto Addition product on soild oxide is contacted with any suitable acid or any acid disclosed herein, the acid such as HCl, Sodium bisulfate or acetic acid.

Method defined in any one of 8. aspect 3-6 of aspect, wherein processing step is treated comprising making to be adsorbed onto Addition product on soild oxide is contacted with any suitable alkali or any alkali disclosed herein, the alkali such as carbonic acid Salt is (for example, Na₂CO₃、CS₂CO₃、MgCO₃), hydroxide is (for example, Mg (OH)₂, NaOH) or alkoxide (for example, Al (O^tPr)3、 Na(O^tBu)、Mg(OEt)₂)。

Method defined in any one of 9. aspect 3-6 of aspect, wherein processing step is treated comprising making to be adsorbed onto Addition product on soild oxide is contacted with any suitable solvent or any solvent disclosed herein, the solvent example Such as solvent containing carbonyl, such as ketone, ester or amide (for example, acetone, ethyl acetate, n,N-Dimethylformamide), alcoholic solvent or water.

Method defined in any one of 10. aspect 3-6 of aspect, wherein processing step is treated comprising that will be adsorbed onto Addition product on soild oxide is heated to the temperature in any suitable temperature or any range disclosed herein, such as 50 DEG C to 1000 DEG C, 100 DEG C to 800 DEG C, 150 DEG C to 600 DEG C or 250 DEG C to 550 DEG C.

Method defined in any one of 11. aforementioned aspects of aspect, further including makes transition metal-ligand complex compound With alkene and carbon dioxide (CO₂) contact to form metal lactone the step of.

A kind of generation α of aspect 12., the method for beta-unsaturated carboxylic acid or its salt, the method includes:

(I) make following contact

(i) transition metal-ligand complex compound；

(II) alkene；

(iii) carbon dioxide (CO₂)；

(iv) diluent；With

(v) treated soild oxide；And

(II) alpha, beta-unsaturated carboxylic acid or its described salt are formed.

Method defined in 13. aspect 11 of aspect or aspect 12, wherein alkene includes any suitable alkene or any Alkene disclosed herein, such as ethylene, propylene or 1- butylene.

Method defined in any one of 14. aspect 1-13 of aspect, wherein α, beta-unsaturated carboxylic acid or its salt include any Suitable α, beta-unsaturated carboxylic acid or any α disclosed herein, beta-unsaturated carboxylic acid or its salt, such as acrylic acid, methyl Acrylic acid, 2- ethylacrylic acid, cinnamic acid, sodium acrylate, Magnesium Acrylate Prepared or Sodium methacrylate.

Method defined in any one of 15. aspect 1-14 of aspect, wherein based on metal lactone (or match by transition metal- The transition metal of body complex compound), α, the molar yield of beta-unsaturated carboxylic acid or its salt is in any range disclosed herein It is interior, for example, at least 5%, at least 10%, at least 15%, at least 25%, at least 50%, at least 100%, at least 150% or at least 200%.

Method defined in any one of 16. aspect 1-15 of aspect, wherein the method further includes following steps: point From α, beta-unsaturated carboxylic acid or its salt, such as use any suitable separation/purifying procedure or disclosed herein point any From/purifying procedure, such as evaporation, distillation or chromatography.

Method defined in any one of 17. aspect 1-16 of aspect, wherein contact procedure and/or forming step are in any conjunction Carried out under suitable pressure or under any pressure disclosed herein, the pressure such as 5psig to 10,000psig or 45psig to 1000psig.

Method defined in any one of 18. aspect 1-17 of aspect, wherein contact procedure and/or forming step are in any conjunction Carried out at a temperature of suitable or at any temperature disclosed herein, such as 0 DEG C to 250 DEG C, 0 DEG C to 95 DEG C of the temperature or 15 DEG C to 70 DEG C.

Method defined in any one of 19. aspect 1-18 of aspect, wherein the meter of treated soild oxide is pressed, Contact procedure carries out under any suitable weight per hour space velocity (WHSV) or any WHSV disclosed herein, institute State WHSV such as 0.05 to 50,1 to 25 or 1 to 5.

Method defined in any one of 20. aspect 1-19 of aspect, wherein treated soild oxide is Louis Acid.

Method defined in any one of 21. aspect 1-19 of aspect, wherein treated soild oxide is that cloth bears department Special alkali.

Method defined in any one of 22. aspect 1-19 of aspect, wherein treated soild oxide is that cloth bears department Special alkali and lewis acid.

Method defined in any one of 23. aspect 1-22 of aspect, wherein treated soild oxide includes any Suitable soild oxide or any soild oxide disclosed herein.

Method defined in 24. aspect 23 of aspect, wherein soild oxide includes Al₂O₃、B₂O₃、BeO、Bi₂O₃、CdO、 Co₃O4、Cr₂O₃、CuO、Fe₂O₃、Ga₂O₃、La₂O₃、Mn₂O₃、MoO₃、Na₂O、NiO、P₂O₅、Sb₂O₅、SiO₂、SnO₂、SrO、TiO₂、 TiO₂、V₂O₅、WO₃、Y₂O₃、ZnO、ZrO₂、K₂O、CaO、La₂O₃Or Ce₂O₃, including its mixed oxide and a combination thereof.

Method defined in 25. aspect 23 of aspect, wherein soild oxide includes silica, aluminium oxide, titanium dioxide Titanium, zirconium oxide, magnesia, boron oxide, calcium oxide, zinc oxide, silica-alumina, by the aluminium oxide of coated with silica, Silica-titania, silica-zirconium oxide, silica-magnesia, aluminium oxide-titanium dioxide, alumina-silica Zirconium, zinc aluminate, alumina-boron oxide, silica-boria, aluminum phosphate, aluminate or phosphate, aluminate or phosphate-silica, aluminium Sour magnesium, titania-zirconia or combinations thereof.

Method defined in 26. aspect 23 of aspect, wherein soild oxide includes magnesium aluminate, calcium aluminate, zinc aluminate, aluminium Sour zirconium, sodium aluminate, magnesia zirconium, sodium oxide molybdena zirconium, calcium oxide zirconium, lanthana chromium, barium monoxide titanium or combinations thereof.

Method defined in the aspect of aspect 27. 23, wherein soild oxide include sodium carbonate, sodium bicarbonate, potassium carbonate, Cesium carbonate or combinations thereof.

Method defined in any one of 28. aspect 1-27 of aspect, wherein treated soild oxide is that calcining is solid Oxide body.

Method defined in any one of 29. aspect 1-28 of aspect, wherein before step (1) or step (I), by place The soild oxide of reason at any suitable temperature or at a temperature in the range of disclosed herein any and calcining It is formed, the temperature is for example, 150 DEG C to 1000 DEG C, 200 DEG C to 750 DEG C or 200 DEG C to 600 DEG C.

Method defined in any one of 30. aspect 1-27 of aspect, wherein treated soild oxide is by gold Belong to the soild oxide of processing.

Method defined in 31. aspect 30 of aspect, wherein being handled before step (1) or step (I) by metal Soild oxide contacts and (simultaneously by the inclusion of making any suitable soild oxide and any suitable metal-containing compound And/or then) calcining method generate.

Method defined in 32. aspect 30 or 31 of aspect, wherein the soild oxide by metal processing includes alkali gold Category, alkaline-earth metal, transition metal or any combination thereof, and by the total weight of the soild oxide by metal processing, lead to Often with the amount in the range of 1 to 30 weight %, 5 to the 25 weight weight of % or 6 to 18 %.

Method defined in any one of 33. aspect 30-32 of aspect, wherein the soild oxide by metal processing includes Alkali metal (by the soild oxide of alkali metal treated), for example, sodium, potassium or caesium with and combinations thereof.

Method defined in any one of 34. aspect 30-32 of aspect, wherein the soild oxide by metal processing includes Alkaline-earth metal (by alkaline-earth metal handle soild oxide), such as magnesium, calcium or barium with and combinations thereof.

Method defined in any one of 35. aspect 30-32 of aspect, wherein the soild oxide by metal processing includes Transition metal (by transition metal handle soild oxide), such as titanium, zirconium, hafnium, tungsten or zinc with and combinations thereof.

Method defined in any one of 36. aspect 1-27 of aspect, wherein treated soild oxide is by gold Belong to the soild oxide of the chemical modification of processing.

Method defined in 37. aspect 36 of aspect, wherein being handled before step (1) or step (I) by metal The soild oxide of chemical modification is generated by a kind of method, and the method includes to make any suitable soild oxide and any Suitable electrophilic anion contact and (while and/or then) calcining to form the soild oxide of chemical modification, and Contact the soild oxide of chemical modification with any suitable metal-containing compound.

Method defined in 38. aspect 36 or 37 of aspect, wherein the solid oxidation of the chemical modification by metal processing Object includes alkali metal, alkaline-earth metal, transition metal or any combination thereof, and by the solid of the chemical modification by metal processing The total weight of oxide, usually with the amount in the range of 1 to 30 weight %, 5 to the 25 weight weight of % or 6 to 18 %.

Method defined in any one of 39. aspect 36-38 of aspect, wherein the solid of the chemical modification by metal processing Oxide includes alkali metal (soild oxide of the chemical modification by alkali metal treated), such as sodium, potassium or caesium and its group It closes.

Method defined in any one of 40. aspect 36-38 of aspect, wherein the solid of the chemical modification by metal processing Oxide include alkaline-earth metal (by alkaline-earth metal handle chemical modification soild oxide), such as magnesium, calcium or barium and A combination thereof.

Method defined in any one of 41. aspect 36-38 of aspect, wherein the solid of the chemical modification by metal processing Oxide include transition metal (by transition metal handle chemical modification soild oxide), such as titanium, zirconium, hafnium, tungsten or Zinc with and combinations thereof.

Method defined in any one of 42. aspect 36-41 of aspect, wherein the soild oxide of chemical modification include and suction The soild oxide of donor anion contact, for example, any soild oxide disclosed herein and any electrophilic yin from Son.

Method defined in the aspect of aspect 43. 42, wherein (a) described soild oxide include silica, aluminium oxide, Silica-alumina, by the aluminium oxide of coated with silica, aluminum phosphate, aluminate or phosphate, heteropoly tungstates, titanium dioxide, oxygen Change zirconium, magnesia, boron oxide, zinc oxide, its mixed oxide or its any mixture；And (b) electrophilic anion includes Sulfate radical, bisulfate ion, fluorine ion, chloride ion, bromide ion, iodide ion, fluorosulfuric acid root, fluoboric acid root, phosphate radical, fluorophosphoric acid Root, trifluoroacetic acid root, trifluoromethanesulfonic acid root, fluorine zirconic acid root, fluotitanic acid root, wolframic acid phosphorus root or any combination thereof.

Method defined in any one of 44. aspect 36-43 of aspect, wherein soild oxide includes aluminium oxide, titanium dioxide Silicon-aluminium oxide, by or mixtures thereof aluminium oxide of coated with silica.

Method defined in any one of aspect of aspect 45. 36 to 44, wherein the electrophilic anion include sulfate radical, Fluorine ion, chloride ion or any combination thereof.

Method defined in any one of 46. aspect 36-44 of aspect, wherein the electrophilic anion includes sulfate radical.

Method defined in any one of 47. aspect 36-44 of aspect, wherein the electrophilic anion include fluorine ion, Chloride ion or both.

Method defined in any one of 48. aspect 36-43 of aspect, wherein the soild oxide of chemical modification includes fluorination Aluminium oxide, chlorinated aluminas, bromided alumina, sulfated alumina, tungstated aluminium oxide, fiuorided silica-alumina, chlorine Change silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorinated silica-oxidation Zirconium, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica Silicon-titanium dioxide, it is fluorinated by the aluminium oxide of coated with silica, fluorination-chlorination by the aluminium oxide of coated with silica, sulphur Acidification by the aluminium oxide of coated with silica, phosphorylation by aluminium oxide of coated with silica or any combination thereof.

Method defined in any one of 49. aspect 36-43 of aspect, wherein the soild oxide of chemical modification includes chlorination Aluminium oxide, fiuorided silica-alumina, it is fluorinated by the aluminium oxide of coated with silica, fluorination-chlorination by silica The aluminium oxide of cladding, sulfated alumina, sulphation by aluminium oxide of coated with silica or combinations thereof.

Method defined in any one of 50. aspect 1-29 of aspect, wherein treated soild oxide includes calcining Sodium carbonate, calcining sodium bicarbonate, calcining potassium carbonate, calcining cesium carbonate or combinations thereof.

Method defined in any one of 51. aspect 1-31 of aspect, wherein treated soild oxide includes to pass through Sodium processing aluminium oxide, by potassium handle aluminium oxide, by caesium handle aluminium oxide, by sodium handle aluminate or phosphate or its Combination.

Method defined in any one of 52. aspect 1-31 of aspect, wherein treated soild oxide includes to pass through The aluminium oxide of magnesium processing, the aluminium oxide by Calcium treatment, aluminium oxide or combinations thereof for being handled by barium.

Method defined in any one of 53. aspect 1-31 of aspect, wherein treated soild oxide includes to pass through The aluminium oxide of zinc processing, the aluminium oxide handled by zirconium, by aluminium oxide of sodium-tungsten processing or combinations thereof.

Method defined in any one of 54. aspect 1-31 of aspect, wherein the treated soild oxide includes Chlorinated aluminas, the sulfated alumina by sodium processing, the tungstated aluminium oxide by sodium processing, process handled by sodium Sodium processing sulphation by the aluminium oxide of coated with silica, by sodium handle the fluorinated oxidation by coated with silica Aluminium, the fiuorided silica-alumina handled by sodium, the fluorination-chlorination handled by sodium are by the oxygen of coated with silica Change aluminium or combinations thereof.

Method defined in any one of 55. aspect 1-54 of aspect, wherein treated soild oxide is with any Surface area in suitable surface area or any range disclosed herein, such as 10m²/ g to 750m²/g、20m²/ g is arrived 500m²/ g or 30m²/ g to 350m²/g。

Method defined in any one of 56. aspect 1-55 of aspect, wherein treated soild oxide is with any Pore volume in suitable pore volume or any range disclosed herein, such as 0.1mL/g to 2.5mL/g, 0.1mL/g are arrived 1.5mL/g or 0.2mL/g to 1.0mL/g.

Method defined in any one of 57. aspect 1-56 of aspect, wherein diluent includes any suitable non-proton molten Agent or any aprotic solvent disclosed herein.

Method defined in any one of 58. aspect 1-56 of aspect, wherein diluent include it is any suitable it is weak coordination or Non-coordinating solvent or any weak coordination disclosed herein or non-coordinating solvent.

Method defined in any one of 59. aspect 1-56 of aspect, wherein diluent includes any suitable molten containing carbonyl Agent or any solvent containing carbonyl disclosed herein, such as ketone, ester or amide are (for example, acetone, ethyl acetate or N, N- dimethyl Formamide).

Method defined in any one of 60. aspect 1-56 of aspect, wherein diluent include any suitable ether solvents or Any ether solvents disclosed herein, such as THF, dimethyl ether, diethyl ether or butyl oxide.

Method defined in any one of 61. aspect 1-56 of aspect, wherein diluent includes any suitable aromatic hydrocarbon Solvent or any aromatic hydrocarbon solvents disclosed herein, such as benzene, dimethylbenzene or toluene.

Method defined in any one of 62. aspect 1-56 of aspect, wherein diluent includes any suitable halogenated aromatic Race's hydrocarbon solvent or any halogenated aromatic hydrocarbon solvent disclosed herein, such as chlorobenzene or dichloro-benzenes.

Method defined in any one of 63. aspect 1-56 of aspect, wherein diluent includes THF, 2,5-Me₂THF, first Alcohol, acetone, toluene, chlorobenzene, pyridine or combinations thereof.

Method defined in any one of 64. aspect 1-63 of aspect, wherein metal lactone (or transition metal-ligand complexing Object) transition metal be the 8th race to the 11st group 4 transition metal.

Method defined in any one of 65. aspect 1-63 of aspect, wherein metal lactone (or transition metal-ligand complexing Object) transition metal be Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt or Au.

Method defined in any one of 66. aspect 1-63 of aspect, wherein metal lactone (or transition metal-ligand complexing Object) transition metal be Ni, Fe or Rh.

Method defined in any one of 67. aspect 1-63 of aspect, wherein metal lactone is nickel lactone, such as any suitable Nickel lactone or any nickel lactone disclosed herein.

Method defined in any one of 68. aspect 1-67 of aspect, wherein metal lactone (or transition metal-ligand complexing Object) ligand be any suitable neutral electron donor group and/or lewis base or any neutral electricity disclosed herein Sub- donor groups and/or lewis base.

Method defined in any one of 69. aspect 1-67 of aspect, wherein metal lactone (or transition metal-ligand complexing Object) ligand be bidentate ligand.

Method defined in any one of 70. aspect 1-69 of aspect, wherein metal lactone (or transition metal-ligand complexing Object) ligand include at least one of nitrogen phosphate and sulfur or oxygen heteroatom.

Method defined in any one of 71. aspect 1-69 of aspect, wherein metal lactone (or transition metal-ligand complexing Object) ligand be any suitable carbene base or any carbene base disclosed herein.

Method defined in any one of 72. aspect 1-69 of aspect, wherein metal lactone, ligand or transition metal-ligand Complex compound is any suitable metal lactone, ligand or transition metal-ligand complex compound, or is any gold disclosed herein Belong to lactone, ligand or transition metal-ligand complex compound.

Claims

1. a kind of generation α, the method for beta-unsaturated carboxylic acid or its salt, the method includes:

(I) make following contact

(i) transition metal-ligand complex compound；

(ii) alkene；

(iii) carbon dioxide (CO₂)；

(iv) diluent；With

(v) treated soild oxide；And

(II) alpha, beta-unsaturated carboxylic acid or its described salt are formed.

2. according to the method described in claim 1, wherein the treated soild oxide include calcining solid oxide, The soild oxide handled by metal, the soild oxide of chemical modification handled by metal or combinations thereof.

3. according to the method described in claim 1, wherein:

The alpha, beta-unsaturated carboxylic acid or its described salt include acrylic acid, methacrylic acid, 2- ethylacrylic acid, cinnamic acid, third Olefin(e) acid sodium, Magnesium Acrylate Prepared, Sodium methacrylate or combinations thereof；And

By the transition metal of the transition metal-ligand complex compound, the α, mole of beta-unsaturated carboxylic acid or its salt Yield is at least 50%.

4. according to the method described in claim 1, wherein:

The alkene includes ethylene；And

The alpha, beta-unsaturated carboxylic acid includes acrylic acid.

5. according to the method described in claim 1, wherein the transition metal of the transition metal-ligand complex compound is that the 8th race arrives 11st group 4 transition metal, and the ligand of the transition metal-ligand complex compound is neutral electron donor group or lewis base (Lewis base)。

6. according to the method described in claim 1, wherein the treated soild oxide includes to pass through alkali metal treated Soild oxide, by alkaline-earth metal handle soild oxide, by transition metal handle soild oxide or its group It closes.

7. according to the method described in claim 1, wherein the treated soild oxide includes to pass through alkali metal treated Chemical modification soild oxide, by alkaline-earth metal handle chemical modification soild oxide, by transition metal at Soild oxide of chemical modification of reason or combinations thereof.

8. according to the method described in claim 1, wherein the treated soild oxide includes the chlorine by sodium processing Change aluminium oxide, by sodium handle sulfated alumina, by sodium handle sulphation by the aluminium oxide of coated with silica, It is handled by sodium fluorinated by the aluminium oxide of coated with silica, the fiuorided silica-alumina by sodium processing, process Fluorination-chlorination of sodium processing is by the aluminium oxide of coated with silica, the aluminate or phosphate handled by sodium or combinations thereof.

9. according to the method described in claim 1, wherein:

The alkene includes ethylene；

The alpha, beta-unsaturated carboxylic acid includes acrylic acid；And

By the transition metal of the transition metal-ligand complex compound, the α, mole of beta-unsaturated carboxylic acid or its salt Yield is at least 75%.

10. a kind of generation α, the method for beta-unsaturated carboxylic acid or its salt, the method includes:

(1) make following contact

(a) metal lactone (metallalactone)；

(b) diluent；With

(c) treated soild oxide；

(3) addition product that processing is adsorbed on the treated soild oxide is to generate the α, β-unsaturation carboxylic Acid or its described salt.

11. according to the method described in claim 10, wherein the processing step is described treated solid comprising making to be adsorbed onto The addition product on oxide body is contacted with acid.

12. according to the method described in claim 10, wherein the metal lactone includes:

Or combinations thereof, wherein Cy be cyclohexyl and^tBu is tert-butyl.

13. according to the method described in claim 10, wherein based on the metal lactone, the α, beta-unsaturated carboxylic acid or its institute The molar yield for stating salt is at least 5%.

14. according to the method for claim 13, in which:

The metal lactone is nickel lactone (nickelalactone)；

The alpha, beta-unsaturated carboxylic acid includes acrylic acid；And

The treated soild oxide changes comprising the soild oxide by metal processing, the chemistry by metal processing The soild oxide or combinations thereof of property.

15. according to the method described in claim 10, wherein:

The treated soild oxide includes the soild oxide by metal processing；And

Before step (1), it is described by metal handle soild oxide by the inclusion of make soild oxide with containing metallization The method for closing object contact and calcining generates.

16. a kind of method for carrying out metal lactone elimination reaction, the method includes:

(1) make following contact

(a) metal lactone；

(b) diluent；With

(c) treated soild oxide；And

(2) alpha, beta-unsaturated carboxylic acid or its salt are formed.

17. according to the method for claim 16, wherein in step (1), the metal lactone and diluent contact The fixed bed of the treated soild oxide.

18. according to the method for claim 17, in which:

Based on the metal lactone, the molar yield of the α, beta-unsaturated carboxylic acid or its salt are at least 5%；And

The metal lactone is nickel lactone.

19. according to the method for claim 16, in which:

The treated soild oxide includes the soild oxide of the chemical modification by metal processing；And

Before step (1), the soild oxide of the chemical modification handled by metal is produced by the inclusion of the following method It is raw: to make soild oxide and electrophilic anion contact and calcine to form the soild oxide of the chemical modification, and make The soild oxide of the chemical modification is contacted with metal-containing compound.

20. according to the method for claim 19, wherein the α, beta-unsaturated carboxylic acid include acrylic acid.